DE1959272B2 - - Google Patents

Description

The present invention relates to a solid bleach mixture and bleach, detergent mixture consisting of a water-soluble hydrogen peroxide addition compound, a compound regulating the release of oxygen from the hydrogen peroxide, a builder salt and optionally a surface-active agent and other customary ones Additives.

The bleach mixture according to the invention is generally in granular or powdery form and has improved bleaching performance. The invention particularly relates to a bleach mixture, the one hydrogen peroxide addition bond, which occurs when it comes into contact with water Formation of hydrogen peroxide decomposes, and a water-soluble copolymer of maleic anhydride and a vinyl compound or a water-soluble salt thereof, particularly a bleach mixture with washing and cleaning properties, which is an organic surfactant, a water-soluble inorganic builder, alone or in combination with a water-soluble organic builder, a hydrogen peroxide addition compound or mixtures of such addition compounds and a water-soluble copolymer of maleic anhydride and a vinyl compound, or a water-soluble salt of this copolymer contains.

It is known that hydrogen peroxide addition compounds or "Peroxyhydr-Ue", for example sodium perborate, decompose in aqueous solution and at high temperature, for. B. above about 80 ⁰ C, quickly release their active oxygen. This rapid release of oxygen can damage textile materials and in particular fine items of clothing, embroidery and the like; it also prevents adequate and effective utilization of the available active oxygen for bleaching purposes.

Many attempts have been made to prevent the rapid release of oxygen in To regulate aqueous solutions in order to avoid damage to the textile materials and to a to achieve optimal bleaching effect. Other attempts have been made with the aim of the release to introduce oxygen at temperatures below 80 ° C with the addition of activators. For this purpose are in the British patent specification 965,672 monoacyl derivatives of hydantoin have been proposed. According to the German patent specification 271 155 is said to be the release of oxygen from

959

Ferocyhydrates at about 80 to 85 C by finishing be regulated by tin derivatives while in the USA.-Palentschrift 2! 21 952 and 2! M! 89 grdalkalirr.etallsiiicate? u suggested for this purpose will. According to German patent specification> 721317, the addition of aminocarboxylic acids (or their salts), which are substituted by more than one carboxyl radical in the position, are recommended.

The tin derivatives form tin (IV) oxide deposits which are insoluble in aqueous solution. while the Erdaikah metal silicates are only sparingly soluble in water: in both cases stains can be found on textile material appear. The use of aminocarboxylic acids is not consistent, as some of the peroxyhydrates are involved © which decompose violently near the boiling point if these acids also in the aqueous solution before-Kegen

The present invention provides a calender mix create effective control of the rate of decomposition of hydrogen peroxide in the aqueous solution and a corresponding utilization of the active oxygen in the mixture allows, whereby a better regulation of the bleaching effect is obtained again than previously Case was.

These and other advantages will become apparent from the following description of the invention.

Hydrogen peroxide addition compounds decompose into aqueous ones. Solution at high temperatures, producing H ₂ O ₂ and salts. This hydrogen peroxide decomposes like-Jer and releases oxygen. The corresponding distribution of the active oxygen is obtained according to the invention by regulating the rate of decomposition of the hydrogen peroxide. The rate of decomposition of the H ₂ O ₂ is also influenced by the pH of the solution, the alkali metal ions present, the temperature of the solution, the hardness of the water and the container materials in which the bleaching is carried out.

It has now been found that the rate of decomposition of the H ₂ O ₂ in an aqueous bleach or bleach and detergent-containing solution can be regulated if a small amount of a water-soluble copolymer of maleic anhydride and a vinyl compound of the formula RCH = HCR, wherein one of the radicals R is a hydrogen atom and the other a C ₁ _4-Alkylätherradikal or a hydrogen atom, or a water-soluble alkali metal or ammonium salt of the copolymer.

The solid bleach mixture or bleach / detergent mixture according to the invention is thereby core uchnet that the mix

a) 0.1 to 5 percent by weight of active oxygen in the form of a water-soluble hydrogen peroxide addition compound,

b) 0.25 to 10 weight percent of a water-soluble copolymer of a vinyl compound of the general formula RCH = CHR wherein one R represents a hydrogen atom and the other radical R is a C ₁ _ ₄ -Alkylätherrest or eir. Means hydrogen atom, and from malcic anhydride or from the alkali metal or ammonium salts of this copolymer as a regulator for the rate of decomposition of the hydrogen peroxide.

c) 10 to 80 percent by weight of a water-soluble inorganic builder salt or mixtures thereof, alone or in combination with a water-soluble organic framework or Mixtures thereof. And

d) 0 to 30 per cent by weight of water-soluble anionic, amphoteric, zwitterionic and nonionic detergents and their mixtures contains as a surfactant.

Preferred detergent and bleach solutions contain 5 to 20 percent by weight of a non-kaiionic detergent, 15 to 60 percent by weight of an inorganic builder salt (preferably sodium tripolyphosphate), 0.5 to 5 percent by weight of active oxygen in the form of a water-soluble inorganic hydrogen peroxide addition compound and 0.5 to 5 percent by weight of a water-soluble copolymer of a vinyl compound of the form! RCH = CHR, in which one radical R is a hydrogen atom and the other radical R is a - OCH ₃ radical or a hydrogen atom, and maleic anhydride or water-soluble alkali metal or ammonium salts of the copolymer. Maleic anhydride vinyl methyl ether is the most preferred copolymer.

The detergent mixture can take any of the various forms available on the market, for example, it can be in granular form, powder form. Flake form and tablet form. The grainy ones and powder form products are preferred.

The degree of polymerization of the copolymer affects its solubility in water. However, it is difficult to determine an absolute value for the upper and lower limits of the degree of polymerization, since this can vary within a wide range. It is essential that the copolymer be appropriately water-soluble under conventional bleaching and washing conditions. There is a recognized relationship between the viscosities of polymeric compounds and their relative molecular weights or degrees of polymerization. These viscosity numbers are very meaningful, and they are often much more readily available than the molecular weights. The copolymers described in the context of the invention are therefore characterized by their specific viscosity or in cP. The most suitable term is given for each copolymer. -Alkylcopolymeren with the maleic anhydride Vinyläiher-C, _ _4, the specific viscosity varies preferably between 0.1 and 6.0 and in particular between 0.2 and 5,0: the specific viscosity is defined as the viscosity of 1 g of the copolymer in 100 cm ^{3 of} methyl ethyl ketone measured in a Cannon-Fenske viscometer at 25 ° C. The viscosity of the maleic anhydride-ethylene copolymer preferably varies between 1.2 and 100 cP when the measurement is made in an aqueous solution with a copolymer content of 2% - the solution is adjusted to a pH of about 10 - in a Brookfield RTV viscometer takes place at 10 rpm and at 25 ° C.

The hydrogen peroxide addition compounds used in the mixtures according to the present invention are organic or, preferably, inorganic in nature. There is a wide variety of these connections. Most of them are produced by crystallization from solutions containing _{H 2} O _2. Others are obtained by drying a slurry containing the appropriate salts and HO, -containing. The most important

Hydrogen peroxide addition compounds are the perborates, ζ. B. the sodium perborate mono- and tetrahydrate. Other perborates that can be used in the context of the present invention are the potassium and ammonium or “real” perborates with the formulas 2HBOj · H ₂ O or 2NH ₄ BO _? H ₁ O. Other valuable hydrogen peroxide additive compounds are the carbonaipetoxyhydrates, e.g. B. 2Na ₂ CO ₃ · 3H ₂ O ₂ , and the phosphate peroxyhydrates. Although a wide variety of sodium, potassium, ammonium, and alkaline earth metal phosphates can be used, sodium pyrophosphate peroxyhydrate _{(Na 4} P ₂ O _{7 -2H 2} O ₂ ) is preferred. The most suitable organic hydrogen peroxide addition compound that can be used in the present invention is urea peroxide [CO (NH ₂ J ₂ · H ₂ O ₂ ], as it is one of the few free flowing dry organic hydrogen peroxide additive compounds.

The following experiments illustrate the effectiveness of the water-soluble miric anhydride vinyl methyl ether and the maleic anhydride-ethylene copolymers in regulating the rate of decomposition of hydrogen peroxide, which is produced by the decomposition of the hydrogen peroxide addition compounds was obtained in aqueous solutions.

Attempt a

ZufünfwäßrigenLösungen (water hardness: 3,4r mol / l Ca ⁺⁺ and Mg ^++, Ca ⁺⁺ ratio. Mg ⁺⁺ about 3: 1), sodium perborate tetrahydrate are corresponding to 200 parts / million Axtivsauerstoff, and 0.5 overall

IO weight percent of a Detergcnsmischung consisting of 10% Natriumalkylbenzolsulional (average C-Atoroanzahl of the alkyl group: 11, S), 2% of a PoIyoxyäthylen-PolyoxypropylenkondcEsats (molecular weight of PolyoxypropyJens: 1750, which makes ethylene polyoxy 80 weight percent of the total weight of the condensate from) 32% sodium tripolyphosphate, 6% sodium sulfate, 2% hydrogenated fish oil fatty acid (average molecular weight: 283), 6% sodium sulfate and 42% moisture (all percentages are percentages by weight).

The first solution is used as a reference solution. One adds to the second and third aqueous solution 1.0 percent by weight or 5.0 percent by weight, calculated on the weight of the detergent mixture, water-soluble maleic anhydride-vinyl methyl ether copolymer to. To the fourth and fifth aqueous solution are added 1.0 percent by weight and 5.0 percent by weight, calculated on the weight of the detergent mixture, water-soluble »maleic anhydride-ethylene copolymer to.

Each aqueous solution is heated and kept at 92 ° C. The active oxygen is determined after 5, 10, 15 and 20 minutes using the permanganate method. '(For details of this method see "Quantitative Inorganic Analysis" by A. Vο ge 1, 3rd edition, 1962, Longmans - London, p. 295; however, 50 cm ^{3 of} a sample solution with 50 cm ³ (0, In) sulfuric acid acidified, and the titration was carried out with a 0.1 η solution of KMnO ₄ until permanent red discoloration occurred ^{; 1 cm 3} _{KMnO 4} corresponds to 16 parts / million active oxygen.) The results are summarized in Table i.

Tabeiie

solution Means for regulating the H ₂ O _r decomposition Weight V. 5 min. available AktivsaomtofT according to IS min. 20 mm. percent*) 78 IO min. 56 52.5 1 . 0 82 65 63 58 2 Maleic anhydride 1.0 71 Vinyl methyl ether copolymer **) 90 80.5 77 3 Maleic anhydride 5.0 85 Vinyl methyl ether copolymer **) 88 59 56 4th Maleic anhydride 1.0 69 Ethylene copolymer ***) 92 85 82.5 5 Maleic anhydride 5.0 89 Ethylene copolymer ***)

*) Percentage by weight of copolymer, calculated on the weight of the detergent mixture.

**) Specific viscosity: about 0.4 (1 g in 100 cm ^{3 of} methyl ethyl ketone at 25 ° C); ratio of the monomers 1: 1. ♦ **) Viscosity: 2 cP in 2% aqueous solution at 25 ° C; Ratio of monomers 1: 1.

Attempt B

The effectiveness of these copolymers compared to a strong complexing agent, for example ethylenediaminetetraacetic acid (EDTA) is illustrated in Table 2. To demonstrate the effect, seven deionized water solutions were made containing 1 part / million ferric ions and 0.5% by weight of the detergent mixture that was ground in the experiment. Each solution was heated to 92 ° C and held at that temperature. Sodium perborate tetrahydrate was then added to each solution, corresponding to 200 parts / million active oxygen, and at the same time 1.0 or 5.0 percent by weight, calculated on the weight of the detergent mixture, of ethylenediaminetetraacetic acid to solutions 2 and 3, of maleic anhydride-vinyl methyl ether copolymer to the solutions 4 and 5 and of maleic anhydride-ethylene copolymer to the solutions 6 and 7 added. The active oxygen available after 5, 10, 15 and 20 minutes was determined for solutions 1, 4, 5, 6 and 7 using the permanganate method, while solutions containing EDTA were determined using the thiosulfate method. (Thiosulfate ^{method a 10 cm 3} sample solution is acidified with Ι, Οη-sulfuric acid; 30 cm ^s of 15% potassium

iodide solution + 100 cm ^{3 of} distilled water are added and the whole is stirred; after 10 minutes in the dark room, titrate with 0.01 n-thiosulphate as soon as

the yellow color disappears, 0.5 g of starch is added and the titration is continued until a colorless solution is obtained will.)

Table 2

solution Means for regulating the heating of water a) b) 1
2 Ethylenediaminetetraacetic acid 3 Ethylenediaminetetraacetic acid 4th Maleic anhydride Vinyl methyl ether copolymer **) 5 Maleic anhydride Vinyl methyl ether copolymer **) 6th Maleic anhydride Ethylene copolymer ***) 7th Maleic anhydride Ethylene copolymer ** *)

Weight 5 min. percent*) d) c) 75 0 66 1 73.5 5 80 1 33 5 79 i 86 5

% available active oxygen after

OMin. 15 minutes. 20 min. el 0 G) 56 46.5 40 54.5 45.5 33 61.5 51 35.5 56 46 39 76.5 72 66.5 65.5 56 48 86 83.5 80.5

·) Percentage by weight of the decomposition control agent calculated on the weight of the detergent mixture. *) Specific viscosity: about 0.4; Ratio of the monomers t: 1. "■ **) Viscosity 2cP in 2% aqueous solution at 25" C: ratio of Mp -.-. Omers I: 1.

Comparing the percentages of EDTA available after 20 minutes is not significant. Of the

Active oxygen in Table 2, EDTA appears when there is a difference in terms of available active oxygen

1% concentration the decomposition of the water 3 ° J _{n of} the 5% maleic anhydride-ethylene copolymer

To strengthen peroxide addition compound, dial-containing solution and the reference solution after

rend the difference in available active 20 minutes is more than 40%.
oxygen between solutions with and without 5%

Attempt C

To compare the effectiveness of maleic acid - the test solutions, however, 1 part / million Cu ^{++ -}

anhydride-ethylene copolymer versus maleic acid ions. The active oxygen, which after 5, 10, 15 and

anhydride polymer was available when the decomposition of H ₂ O _{2 was} available for 20 minutes, was

The medium in aqueous solutions was determined by five manganate methods. The results are in

Experiments as described in the section "Experiment B", Table 3 indicated,
carried out. Contained instead of Fe ^{+ + + ions}

Table 3

solution Means for regulating the H, O ₂ decomposition Weight % 5 min. available active oxygen 15 minutes. 20 min. prozeni j 37 10 min. 17.5 13th 1 0 56.5 23 28 22.5 2 Maleic anhydride 1 38 Ethylene copolymer **) 74.5 55 46.5 3 Maleic anhydride 5 60.5 Ethylene copolymer **) 43.5 21 15.5 4th Maleic anhydride polymer ***) 1 55 28 27.5 21.5 5 Maleic anhydride polymer * * *) 5 35.5

*) Percentage by weight of the decomposition agent, calculated on the weight of the detergent mixture. * ·) Specific viscosity: about 0.4; Ratio of monomers 1: 1. ·· *) Viscosity 2cP in 2% aqueous solution at 2S ° C.

T
r
ι
ι

According to table 3, solution 1, copper ions strengthen solution 2, both after 5,10,15 or 20 mi

Cu ^{+ +} the hydrogen peroxide decomposition. The grooves, and in spite of the greater amount of them

maleic anhydride polymer settling-regulating effect,

mers, as compared with the effect caused by the ₆₅ Experiment D
Maleic anhydride-ethylene copolymer is obtained,

rather low, since the percentages of available Dk surprising effect of the copolymers of

Active oxygen in solution 5 are lower than that of maleic anhydride and a vinyl compound of

409507/406

Surface active

Medium ¹ )

Builder ² )

composition III IV V Vl I. I! 10 10 15th 15th 10 10 45 45 40 40 45 45

type defined above in detergent solutions containing hydrogen peroxide addition compounds also from the following tables.

The stability of sodium perborate tetrahydrate is extremely sensitive to an increase in pH, particularly in the range of 8.5 to 9 ° C and above. It is also known that the rate of decomposition of H ₂ O _{2 increases} with increasing pH and is catalyzed by copper and iron ions. To simulate these adverse conditions, aqueous solutions of deionized water were prepared to which Cu ^{u +} ions and Fe ^{+ + +} ions were added. The concentration of the bleach and detergent mixture. as indicated below in each solution. was 0.6 percent by weight. The pH of these aqueous solutions was above 8.5.

The following blends (Table 4) were dissolved in aqueous solutions (Figures are percentages by weight) tested, the 0.5 parts / million Cu ⁺⁺ - ions and contained 0.5 parts / million Fe ^{+ + +} ions.

Table 4

Peroxyhydrate ³ )
Copolymer ⁴ ) ..

Remainder ⁵ ).

composition

Il

5 5

III

35

10

IV

35 5 5

25th

20th

³ I peroxyhydrate: sodium perborate tetrahydrate.

*) Copolymer: a maleic anhydride - vinyl methyl ether im Ratio 1: 1 with a specific viscosity of 04 (1 g in 100 cm 'methyl ethyl ketone solution at 25 C).

*) Remainder: sodium sulfate.

The percentages of after 10 and 20 minutes in the aqueous, up to 92. ^{Solutions of available active oxygen held at r} C, measured by the customary permunganate method, are as follows:

Table 5

Time

10 mins.
20 minutes,

50 34

Mixture II I III I IV I V I Vl

79 73

66 49

77 67

12 80

K)! 75

Table 5 shows the effectiveness of the maleic anhydride-vinyl methyl ether copolymer in solutions II, IV and VI.

') Surface active agent, consisting of

a) 65.5 percent by weight of a sodium straight chain alkylbenzenesulfonate (Average number of carbon atoms in the alkyl radical 11.8).

b) 21 percent by weight hydrogenated fish oil (average molecular weight: 285),

c) 13.5 percent by weight of a tallow alcohol - ethylene oxide condensate (average number of oxide units: 11),

except for the case of mixtures V and VI in which the surfactant is sodium 3- (N, N-dimethyl-N-coconut alkylammonio) -2-hydroxypropane-1-sulfonate. ² ) Builder:

a) in the case of mixtures I and II: sodium pyrophosphate.

b) in the case of mixtures III and IV: a mixture of sodium tripolyphosphate and sodium ethylenediamine tetraacetate in a ratio of 3: 1,

c) in the case of mixtures V and VI: sodium tripolyphosphate.

35

40

45 attempt E

The surprising results that are achieved within the scope of the present invention can also be seen from the following series of tests (Tables 6 and 7), the available active oxygen being measured after 20 minutes using the customary permanganate method. The concentration of the hereinbelow indicated detergent mixture was 0.6 weight percent, the temperature of the solution was 92 ⁰ C, and as water, deionized water was used, the Cu ^{+ +} - and Odei Fe ^{+ + +} ions were added.

Tabel

Surfactant ⁶ ).

Builder ⁷ )

Peroxyhydrate ⁸ )

Copolymer ⁹ )

Remainder ¹⁰ )

mixture

VII

10 60 20 0 10

VIII

10 60 20

3 7

25th
35
30th
0
10

Xl

25th

35

30th

XII XHI XIV

10
45
35
0 10

10

45

35

XV

35 45 10 0 10

') Surface-active center !: as for mixtures I to IV of the table

⁷ ) Builder: sodium tripolyphosphate

^s \ Peroxvhvdrat: Sodium perborate tetrahydrate

⁹ ^ Copolymer: a maleic anhydride-vinylmethyl ether copolymer in the ratio 1.1 mn a specific viscosity of 0.4.

¹⁰ I remainder: sodium sulfate.

The percentage of available active oxygen after 20 mini / .en at 92 ⁰ C was:

Table 7 pollution

1 part / million Cu ⁺⁺

1 part / million Fe ^{++ +}

0.5 parts / million Cu ^{+ +} and
0.5 parts / million Fe ^{++ +} ...

VIII IX X mixture XIl XIIl XIV XV VII 25th 60 3 XI 39 5 13th 10 7th 88 89 24 13th 85 24 78 69 41 - - - 60 - 8th 35 13th - -

The surprising effectiveness in regulating the H ₂ O ₂ decomposition rate by the copolymer becomes clear when the results of mixture VII with those of mixtures VIII and IX or those of mixture X with those of mixtures XI and XII or those of mixture XIII with those of Mixture XIV or the results as obtained with Mixture XV are compared with the results of Mixture XVI.

The surfactant used in the mixtures according to the present invention includes: anionic, amphoieric, zwitterionic and nonionic detergents and mixtures thereof. Suitable substances are below enumerated:

a) The anionic detergent that can be used in the mixtures according to the invention can be both a soap and a non-soap detergent compound. Examples of suitable soaps are the sodium, potassium, ammonium and alkylammonium salts of higher fatty acids (C ₁₀ -C ₂₀ ). Examples of anionic organic non-soap detergent compounds are the water-soluble alkali metal salts or organic sulfuric acid reaction products which contain in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical consisting of groups comprising sulfonic acid and H sulfuric acid ester radicals. (The term "alkyl" includes the alkyl group of higher acyl radicals.) Important examples of the synthetic detergents which can form part of the mixtures according to the invention are the sodium or potassium alkyl sulfates, in particular those which are obtained by sulfating higher alcohols (Cg-C ₁₈ carbon atoms); Sodium or potassium alkyl benzene sulfonates such as described in U.S. Patents 2,220,009 and 2,477,383, wherein the alkyl group contains from about 9 to about 15 carbon atoms; Sodium alkyl glyceryl ether sulfonates, particularly those ethers of the higher alcohols derived from tallow and coconut oils; Sodium coconut oil fatty acid mor.oglyceride surfates and sulfonates; Sodium or potassium salts of sulfuric acid esters of the reaction product of 1 mole of a higher fatty alcohol (e.g. tallow or coconut oil alcohols) and about 1 to 6 moles of ethylene oxide; Sodium or potassium salts before alkylphenolethylene oxide ether sulfate with about 1 to about 10 units of ethylene oxide per molecule, in which the alkyl radicals contain about 9 to about 12 carbon atoms; the reaction product of fatty acids with 10 to 22 carbon atoms with taurines or isethionic acid. which is neutralized with sodium hydroxide, and other products known per se, a number of which are described in U.S. Patents 2,48692. 2486922 and 2396278 are specifically described.

b) Nonionic synthetic detergents can

Ij generally as compounds of aliphatic or alkyl

aromatic nature are addressed, which in

Do not ionize aqueous solutions. Examples of this

are compounds produced by condensation of

Ethylene oxide is formed with a hydrophobic base, which by condensation of propylene oxide with

Propylene glycol is formed, being the hydrophobic

Section of the molecule has a molecular weight of

has about 1500 to 1800 and the polyoxyethylene

content makes up about 50% of the total weight of the condensation product.

Other suitable nonionic synthetic detergents include:

1. The polyethylene oxide condensates of alkylphenols, z. B. the condensation products of alkylphenols with an alkyl group containing et wa 6 to 12 carbon atoms having, with ethylene oxide, the ethylene oxide being present in amounts ranging from 10 to 25 mol Correspond to ethylene oxide per mole of alkylphenol.

2. Nonionic synthetic detergents resulting from the condensation of ethylene oxide with the

Derive the product that is formed when propylene oxide and ethylenediamine are converted. For example are compounds containing about 40 to about 80 percent by weight polyoxyethylene, a total molecular weight from about 5000 to about 11,000 and in the reaction of ethylene oxide groups with a hydrophobic base formed by the reaction product of ethylenediamine and excess Propylene oxide is formed, with the hydrophobic base having a molecular weight on the order of magnitude from 2500 to 3000 is satisfactory.

3. The condensation product of aliphatic alcohols having 8 to 22 carbon atoms, in particular 10 to 18 carbon atoms, with 10 to 30 moles of ethylene oxide per mole of alcohol.

4. Long-chain tertiary amine and phosphine oxides, corresponding to the general formula R ₁ R ₂ R ₃ X - ♦ O, in which X is a nitrogen or phosphorus atom, R _{1 is} an alkyl radical with about 8 to 18 carbon atoms and R ₂ and R _{3 are} each methyl - or mean ethyl radicals. The arrow in the formula is a common representation of a semi-polar bond. Examples of such oxides suitable for use in the present invention include dimethyldodecylamine oxide, dimethyloctylamine oxide, dimethyldodecylphosphine oxide, and ethylmethyltetradecylphosphine oxide.

5. Dialkyl sulfoxides, which correspond to the following general formula, RR'S - ► O, where R is an alkyl,

Alkenyl, β- or γ-monohydroxyalkylreat or an alkyl or β- or γ -monohydroxyalkyl radical with one or two further oxygen atoms in the

Chain denotes where the group R has 10 to 18 carbon atoms in chain length and in which R 'symbolizes methyl or ethyl. Examples of suitable sulfoxide compounds are dodecyl methyl sulfoxide and 3-hydroxytridecylmethyl sulfoxide.

c) Ampholytic synthetic detergents can generally be used as derivatives of aliphatic secondary and tertiary amines are described, in which the aliphatic The remainder can be straight-chain or branched and in which one of the aliphatic substituents, for example 8 to 18 carbon atoms and one having an anionic water-solubilizing group. Examples for compounds falling under this definition are sodium 3-dodecylaminopropionate and sodium 3-dodecylaminopropanesulfonate.

d) Zwitterionic synthetic detergents can generally be used as derivatives of aliphatic quaternary Ammonium compounds are described in which the aliphatic radical can be straight-chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains one having anionic water-solubilizing group. Examples of compounds falling under this definition fall are 3- (N, N-DimethyI-N-hexadecylammonio) -propane-1 sulfonate and 3- (N, N-Dimethy! -N-bexadecylammonio) -2-hydroxypropane-l-sulfonate, especially because of their excellent detergent characteristics to be favoured.

The anionic, nonionic, ampholytic and zwitterionic detergents mentioned above can be used singly or in combination in the practice of the present invention will. The above examples are merely specific illustrations of the various detergents represent, which can be used in the context of the invention.

The builders that can be used in the mixtures according to the invention include those water-soluble inorganic alkaline builder salts, as such or in combination with organic alkaline builder salts can be used. Suitable inorganic builder salts are the soluble polyphosphate salts, such as sodium or potassium pyrophosphate and tripolyphosphate, furthermore Sodium silicate, sodium carbonate and sodium borate. Suitable organic builder salts are the sodium and potassium ethylenediamine tetraacetate and nitriloacetate, the sodium and potassium lower alkyl diphosphonates, such as trisodium ethylene 1-hydroxy-1,1-diphosphonate, the alkali metal salts of phytic acids such as sodium phytate and mixtures thereof inorganic and organic builder salts.

The detergent mixtures preferably contain a builder and a detergent in a weight ratio from about 1: 3 to about 10: 1. The preferred builder to detergent ratio is about 1: 2 to about 5: 1.

The finished detergent formulations according to the invention often contain small amounts of materials added, which make the product more attractive. The following are examples of this. Sodium carboxymethyl cellulose can be added in small amounts to inhibit soil redeposition. A yellowing inhibitor such as benzotriazole or ethylene thiourea can also be used in amounts up to about 2% are added. Ruorescent substances, perfumes and dyes, although not essential Components of the mixtures according to the invention are.

can also be added in small quantities. You can also use small amounts of one alkaline material or small amounts of alkali, such as sodium hydroxide or potassium hydroxide, Add complementary pH-adjusting agents to hIs.

Other suitable additives that are to be mentioned are Bacteriostats, Sodium Sulphate and Sodium Carbonate, Bactericides and Enzymes.

In general, corrosion inhibitors are also used

ίο added. Soluble silicates are highly effective inhibitors and in certain approaches according to the invention can be added in amounts of about 3 to about R%. Alkali metal, preferably potassium or sodium silicates with a weight ratio of SiO ₂ : M ₂ O of 1: 1 to 2.8: 1 can be used. M means sodium or potassium in this ratio. A sodium silicate having a SiO ₂ : Na ₂ O ratio of about 1.6: 1 to 2.45: 1 is particularly preferred for reasons of economy and effectiveness.

In view of the increasing interest in detergent mixtures containing the builder with oxygen bleaches in practically all washing and cleaning tasks and especially when washing wipes find it makes a very significant contribution to this invention that an improved detergent product was created, which gives bleach values that contain those of a conventional builder Product because of the corresponding utilization of the active oxygen in the bleach and Washing liquids are superior, the copolymers having whiteness retention properties the washing solutions have a positive effect. The following examples are used for processing.

realization of the invention. All percentages in the examples are percentages by weight.

example 1

A granular bleach and detergent mix. as described below is by slurry the surfactants and builders, spray drying the slurry and Mixing in the perborate, copolymer and perfume made into a spray-dried product. The end product consists of:

12% sodium alkyl benzene sulfonate (average chain length 11.8), 5% hydrogenated fish oil fatty acids (average molecular weight 285). 3% tallow alcohol ethylene oxide

(average content of ethylene units: 11), 35% sodium tripolyphosphate, 5% sodium silicate,
3% maleic anhydride vinyl methyl ether

copolymer (specific viscosity: about 0.4), 30% sodium perborate tetrahydrate; Remainder: sodium sulfate, carboxymethyl cellulose; Perfume.

The maleic anhydride vinyl methyl ether copolymer (ratio of the monomers 1: 1) can by Maleic anhydride-ethylene copolymer are replaced on the basis of a corresponding percentage, or with the disodium salts of one or both products.

The sodium perborate tetrahydrate can be replaced by the carbonate peroxyhydrate, 2Na ₂ CO ₃ 3H ₂ O ₂ , or using a corresponding percentage

i 959

be replaced by the sodium pyrophosphate peroxyhydrate, Na ₄ P ₂ O ₇ · 2H ₂ O ₂ .

Example 2

A detergent mix is made by slurrying the detergent and builder, spray drying the slurry and addition of copolymer, perfume and perborate to the spray dried Product manufactured. The end product consists of:

6% sodium 3- (N, N-dimethyl-N-tetradecyl-

ammonio) -2-hydroxypropane-1-sulfonate, 40% sodium tripolyphosphate, 25% sodium perborate tetrahydrate, 15% sodium sulfate, moisture, perfume, 5% maleic anhydride-vinyl methyl ether copolymer
(specific viscosity: 0.4), 9% sodium silicate.

The percentage of available AktivsauerstofT in a wash solution containing 0.5 percent by weight of the detergent mixture, and was heated to 92 ⁰ C, was, after the usual Permanganatmethode after 10 minutes 77% and after 20 minutes 6.5%.

Heavily soiled clothes that were washed with the detergent mix for 30 minutes excellently cleaned and bleached. Other suitable mixtures are:

15th

Example 3

6% C ₁₁ _ ₁₃ alkyl benzene sulfonate (sodium salt), 3% tallow alkyl sulfate (sodium salt), 4% polyoxyethylene-polyoxypropylene condensate (molecular weight of the polyoxypropylene 1750; polyoxyethylene: 60 weight percent), 2% hydrogenated fish oil fatty acid

(average molecular weight 285), 40% sodium pyrophosphate, 30% sodium perborate tetrahydrate,

5% maleic anhydride-ethylene copolymer, 10% sodium sulfate, moisture, carboxymethyl cellulose, brightener.

Example 4

5% tallow alcohol-ethylene oxide condensate

(average number of oxide units: 11), 2% hydrogenated fish oil fatty acid

(average molecular weight 285), 40% sodium tripolyphosphate, 30% sodium perborate tetrahydrate, 2% maleic anhydride vinyl methyl ether, 16% sodium sulfate, 5% perfume, sodium silicate, moisture.

Example 5

8% sodium Qj g-alkylbenzenesulfonate, 4% polyoxyethylene-polyoxypropylene condensate (molecular weight of polyoxypropylene 1750; Polyoxyethylene: 80 percent by weight). 27% sodium tripolyphosphate, 8% sodium pyrophosphate, 20% sodium pyrophosphate peroxyhydrate, 2% maleic anhydride vinyl methyl ether

copolymer,
6% sodium silicate,

25% sodium sulfate and small amounts of carboxymethyl cellulose and perfume.

B e i s ρ i e 1 6

5% sodium salt of Q ₂ _, ₈ fatty acids. 10% nonylphenol-ethylene oxide condensate (average number of oxide units: 8), 40% sodium tripolyphosphate,

25% sodium perborate tetrahydrate, 5% maleic anhydride vinyl methyl ether, Remainder: sodium sulfate, moisture, sodium silicate, carboxymethyl cellulose.

Claims (1)

Patent claims: 1. Solid bleach blend and bleach. Detergent mixture consisting of a water-soluble hydrogen peroxide addition compound, a compound regulating the release of oxygen from the hydrogen peroxide, one Builder salt and optionally a surface-active agent and other customary additives, characterized, that the mix a) 0.1 to 5 percent by weight of active oxygen in the form of a water-soluble hydrogen peroxide addition compound, ' ⁵ b) 0.25 to 10 percent by weight of a water-soluble copolymer of a vinyl compound the general formula RCH = CHR, wherein one R represents a hydrogen atom and the other radical R is a C ₁ _ ₄ -Alkylätherrest or a hydrogen atom, and maleic anhydride, or from the alkali metal or ammonium salts of this copolymer as a controller for the rate of decomposition of hydrogen peroxide, c) 10 to 80 percent by weight of a water-soluble inorganic builder salt or mixtures thereof, alone or in combination with a water-soluble organic Builder salt or mixtures thereof, and d) 0 to 50 percent by weight of water-soluble anionic amphoteric, zwitterionic and nonionic detergents and mixtures thereof contains as a surfactant. 2. Mixture according to claim 1, characterized in that that they are out a) 0.5 to 5 percent by weight of active oxygen in the form of a water-soluble inorganic Hydrogen peroxide addition compound, b) 0.5 to 5 percent by weight of a water-soluble one Copolymer of a vinyl compound of the general formula RCH = CHR, wherein one radical R is a hydrogen atom and the other radical R is a - OCH ₃ radical or a hydrogen atom, and from a maleic anhydride or from the alkali metal or ammonium salts of maleic acid, c) 15 to 60 percent by weight of an inorganic builder salt and d) 5 to 20 percent by weight of a water-soluble, non-cationic detergent consists. 3. Mixture according to claim 1 or 2, characterized in that it contains a reaction product of sulfuric acid with C, ₀ _ ₁₈ fatty alcohols or C, o_, ₄ -alkylbenzenes or alkali metal salts of the Reakliunsproclukls as surface-active agent. Mixture according to claim 1 or 2, characterized in that it contains the active oxygen in the form of niitrium perborate tetrahydrate or in the form of sodium pyriphosphate peroxyhydrate. 5. Mixture according to claim 1 or 2, characterized in that it is ais Gerüststoffsa! Z sodium tripolyphosphate contains. 6. Mixture according to claim 1 or 2, characterized in that it is a copolymer of Vinyl methyl ether and maleic anhydride as regulators for the rate of decomposition of Contains hydrogen peroxide.